Solid State Ionics最新文献_第3页

A hydration chamber for La-doped ceria ceramics with crystal hydrate-stabilized water vapor pressure 具有晶体水合稳定水蒸汽压的掺镧铈陶瓷水合室

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-08 DOI: 10.1016/j.ssi.2025.117084

Or Ben Zion , Isaac Abrahams , Ellen Wachtel , Xiao-Dong Zhang , Xin Guo , Igor Lubomirsky , David Ehre

Conventional methods for hydrating bulk ceramic samples at relatively low pressures (<5 atm of water steam) often fail to achieve significant hydration because of kinetic barriers and mechanical failures, the latter primarily due to inhomogeneous lattice expansion accompanying hydration. We propose a small, high-pressure chamber that can reach tens of atm of steam pressure without the necessity of operating a high-pressure/high temperature autoclave or pressure vessel. The chamber takes advantage of the dehydration of CoSO₄·7H₂O powder to stabilize water partial pressure up to 100 atm. This facilitates effective hydration at moderate temperatures, producing crack free pellets under reproducible conditions. Using La_0.45Ce_0.55O_1.775 ceramics (LCO45) as a test case, we demonstrate that hydration in the chamber with

P_{H_{2} O} \approx 56

atm produces at least ten times more water incorporation than hydration with 1 atm steam (38.5 % vs 3.7 % of oxygen vacancies filled) at the same temperature, 673 K, while requiring approximately one-tenth of the time (5 h vs 48 h). X-ray powder diffraction reveals an expansion of 0.43 % in the fluorite lattice parameter of LCO45 ceramics hydrated in the chamber. Chamber hydration increased conductivity in the temperature range 383–463 K by ca. two orders of magnitude compared to the dry pellet, the increase attributable to proton conductivity. The hydration protocol described below does not allow independent setting of temperature and pressure; however, due to its simplicity and economic accessibility, it may provide a viable method for achieving a high degree of hydration in ceramic samples while, at the same time, preserving their mechanical integrity.

在相对较低的压力下（<；5 大气压的水蒸气）水化大块陶瓷样品的传统方法往往由于动力学障碍和机械故障而无法实现显著的水化，后者主要是由于水化过程中不均匀的晶格膨胀。我们提出了一种小型高压室，可以达到数十atm的蒸汽压力，而无需操作高压/高温高压灭菌器或压力容器。该室利用CoSO₄·7h2o粉体的脱水作用，将水分压稳定在100 atm以下。这有利于在中等温度下有效的水化，在可重复的条件下生产无裂纹的颗粒。使用La0.45Ce0.55O1.775陶瓷（LCO45）作为测试案例，我们证明了在相同温度（673 K）下，PH2O≈56 atm的水化室中，水化产生的水掺入量至少是1 atm水化室的十倍（38.5 % vs 3.7 %的氧空位填充），而所需的时间约为十分之一（5 h vs 48 h）。x射线粉末衍射结果表明，水化LCO45陶瓷的萤石晶格参数膨胀了0.43 %。在383-463 K温度范围内，与干燥球团相比，腔室水化提高了大约两个数量级的电导率，这是由于质子电导率的增加。下面描述的水化方案不允许独立设置温度和压力；然而，由于其简单性和经济可及性，它可能提供一种可行的方法来实现陶瓷样品的高度水化，同时保持其机械完整性。

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引用次数: 0

Crossover from insulating into solid electrolyte behavior in bulk CaSO4⋅0.5H2O material due to ion exchange processes induced by high-temperature treatment with orthophosphoric acid 正磷酸高温处理诱导的离子交换过程导致大块CaSO4·0.5H2O材料从绝缘过渡到固体电解质行为

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-07 DOI: 10.1016/j.ssi.2025.117098

Ivan Nikulin, Tatiana Nikulicheva, Vitaly Vyazmin, Oleg Ivanov, Nikita Anosov, Olga Telpova

CaSO₄-based citrogypsum was used to prepare bulk samples of calcium sulfate hemihydrate (CaSO₄·0.5H₂O). To alter composition and improve conductivity, the samples were treated at 95 °C in 85 wt% orthophosphoric acid for 1 to 15 min. Within <1 min, CaSO₄·0.5H₂O transforms into CaSO₄·2H₂O. At longer times, partial dehydration converts part of the CaSO₄·2H₂O. back into CaSO₄·0.5H₂O, yielding a two-phase mixture. Acid treatment induces cation (2H⁺ ↔ Ca²⁺) and anion ((HPO₄)²⁻ ↔ (SO₄)²⁻) exchange, producing a transition from insulating to solid-electrolyte behavior. Weakly bound H⁺ ions, incorporated either by Ca²⁺ substitution or via (HPO₄)²⁻ residues, act as mobile charge carriers and enable proton conductivity. Residues that release protons convert to (PO₄)³⁻ groups, which can be displaced in an alternating field, generating ionic polarization and relaxation currents. The combined effects of H⁺ mobility and (PO₄)³⁻ polarization produce two arcs in AC impedance spectra. Conductivity parameters extracted with the Cole model strongly depend on sample composition.

用CaSO4基柠檬酸石膏制备半水合硫酸钙（CaSO4·0.5H2O）散装样品。为了改变组成和提高电导率，样品在85 wt%的正磷酸中于95°C下处理1至15分钟。在1 min内，CaSO4·0.5H2O转化为CaSO4·2H2O。在较长的时间内，部分脱水转化了部分CaSO4·2H2O。还原为CaSO4·0.5H2O，生成两相混合物。酸处理诱导阳离子（2H+↔Ca2+）和阴离子(（HPO4)2−↔（SO4）2−）交换，产生从绝缘到固体电解质行为的过渡。弱结合的H+离子，通过Ca2+取代或通过（HPO4）2 -残基结合，作为移动电荷载体并使质子电导率。释放质子的残基转化为（PO4）3 -基团，这些基团可以在交变场中移位，产生离子极化和弛豫电流。H+迁移率和（PO4）3−极化的共同作用在交流阻抗谱中产生了两条弧。用Cole模型提取的电导率参数强烈依赖于样品组成。

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引用次数: 0

Ion-dependent electrochemical behavior in shear-structured tungsten oxides 剪切结构钨氧化物中离子依赖的电化学行为

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-05 DOI: 10.1016/j.ssi.2025.117095

Vincenzo J. Musicó , Noah P. Holzapfel , Menghang Wang , Wan-Yu Tsai , Tatiana Proksch , Boris Kozinsky , Nina Balke , Veronica Augustyn

The demand for high-energy and high-power energy storage devices motivates the search for electrode materials with both high capacity and fast ion transport. One class of materials that could achieve such performance are oxides containing crystallographic shear (CS) planes. Here, we compare the structural dynamics of tungsten trioxide (WO₃) and its oxygen deficient, CS Magnéli phase (WO_2.9) during electrochemical insertion of H⁺ and Li⁺ ions using a combined experimental and computational study. We found that WO₃ inserts more H⁺ per formula unit than WO_2.9 yet operando electrochemical atomic force microscopy shows more deformation in WO_2.9 than WO₃ per inserted H⁺. In contrast, WO_2.9 accommodates ∼0.2 more Li⁺ per formula unit than WO₃ and has higher Li⁺ diffusion and better rate capability. Operando electrochemical X-ray diffraction shows that Li⁺ insertion into WO_2.9 leads to lattice contraction and 5 % volume change up to Li_0.6WO_2.9 followed by a zero-strain region up to Li_1.4WO_2.9. We find that the presence of CS planes, and its effect on octahedral tilting, lead to different outcomes depending on the inserting ion: while octahedral tilting and lack of CS planes promote H⁺ insertion into WO₃, their absence in WO_2.9 favor Li⁺ insertion. We propose that the presence of CS planes impart structural rigidity, enabling higher capacity, improved rate capability, and enhanced cyclability during Li⁺ insertion but remove favorable bridging oxygen sites for H⁺ insertion.

对高能、高功率储能器件的需求促使人们寻找具有高容量和快速离子传输的电极材料。一类可以达到这种性能的材料是含有晶体剪切（CS）平面的氧化物。本文采用实验和计算相结合的方法，比较了三氧化钨（WO3）及其缺氧相CS magnacimri （WO2.9）在H+和Li+离子电化学插入过程中的结构动力学。我们发现WO3在每个分子式单位中插入的H+比WO2.9多，但电化学原子力显微镜显示WO2.9中的变形比WO3中插入的H+更大。相比之下，WO2.9比WO3每个配方单位多容纳~ 0.2个Li+，并且具有更高的Li+扩散和更好的速率能力。Operando电化学x射线衍射表明，Li+插入到WO2.9中导致晶格收缩，到Li0.6WO2.9时体积变化5%，到Li1.4WO2.9时出现零应变区。我们发现CS平面的存在及其对八面体倾斜的影响，根据插入离子的不同导致了不同的结果：八面体倾斜和CS平面的缺乏促进了H+插入到WO3中，而WO2.9中CS平面的缺失则有利于Li+的插入。我们提出CS平面的存在赋予结构刚性，在Li+插入过程中实现更高的容量，改进的速率能力和增强的可循环性，但去除有利于H+插入的桥接氧位点。

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引用次数: 0

Determining the optimal operating conditions of SOFCs electrolytes based on evolution of their electronic transport number with temperature and oxygen partial pressure: A case study of the Ce0.9Gd0.1O2-δ electrolyte 基于电子输运数随温度和氧分压的变化确定SOFCs电解质的最佳工作条件——以Ce0.9Gd0.1O2-δ电解质为例

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-03 DOI: 10.1016/j.ssi.2025.117097

E. Bonnet , M.C. Steil , J. Fouletier , L. Gaillard , B. Rousseau , C. Jourde , J.-M. Bassat , P.-M. Geffroy

Optimizing the performance of Solid Oxide Fuel Cells (SOFCs) or Solid Oxide Electrolysis Cells (SOECs) necessitates a thorough understanding of the electrolytes' transport properties under the device's operating conditions, whether through experimental data or established transport laws. This study investigates the electrical properties of Gd-doped ceria as a potential electrolyte material for SOFC applications. The electrical behavior of Gd-doped ceria was analyzed over a broad range of oxygen partial pressures (from 10⁻³⁶ to 1 bar) and temperatures (200 °C to 900 °C) to establish the Patterson diagram, i.e., the variation of the total electrical conductivity as a function of the oxygen partial pressure (on logarithmic scales) for various temperatures. Additionally, the average transport number of the Gd-doped ceria electrolyte was evaluated under varying oxygen partial pressure gradients and temperatures using a specific semi-permeation method and compared with data derived from the Patterson diagram. The results collected in this study indicate that the use of Gd-doped ceria as an SOFC electrolyte requires precise control of oxygen partial pressure (particularly below 10⁻²⁴ bar at 600 °C) or the hydrogen-to-water ratio at the hydrogen electrode to prevent efficiency degradation of the electrochemical system and to determine optimal operating conditions.

优化固体氧化物燃料电池（sofc）或固体氧化物电解电池（soec）的性能，需要通过实验数据或已建立的传输规律，全面了解设备工作条件下电解质的传输特性。本研究探讨了作为SOFC应用的潜在电解质材料的钆掺杂二氧化铈的电学性质。在广泛的氧分压（从10−36到1 bar）和温度（200°C到900°C）范围内分析了gd掺杂的二氧化铈的电学行为，以建立帕特森图，即总电导率的变化作为氧分压（在对数尺度上）在不同温度下的函数。此外，使用特定的半渗透方法评估了不同氧分压梯度和温度下gd掺杂的铈电解质的平均输运数，并与帕特森图的数据进行了比较。本研究收集的结果表明，使用gd掺杂的二氧化铈作为SOFC电解质需要精确控制氧分压（特别是在600°C时低于10−24 bar）或氢电极上的氢水比，以防止电化学系统的效率下降并确定最佳操作条件。

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引用次数: 0

Room temperature, solid-state Ca ion-exchange in Na0.67Mn0.72Mg0.28O2 室温下，固态Ca离子在Na0.67Mn0.72Mg0.28O2中交换

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 DOI: 10.1016/j.ssi.2025.117085

John-Joseph Marie , Jun Chen , Shengda D. Pu , Alex W. Robertson , Robert A. House , Peter G. Bruce

Ion-exchange is an important route to achieve partial or complete substitution of alkali ions into intercalation cathodes for alkali-ion batteries. In Na-ion cathodes, the partial substitution of Na for large, charge dense pillar ions, such as Ca²⁺, could help alleviate the detrimental structural transitions that these cathodes undergo during desodiation. Typically, ion-exchange is achieved by heating the cathode powder in the presence of a substantial molar excess of alkali halide salt in solution. Here, we successfully demonstrate ion-exchange of Ca²⁺ for Na⁺ in Na_0.67Mn_0.72Mg_0.28O₂ by simple mechanical mixing of powders with the proper molar amount of CaI₂ under ambient conditions. The reaction proceeds in the solid-state at room temperature via the formation of crystalline hydrates of CaI₂ which form spontaneously with moisture in the air. Ca²⁺ is uniformly incorporated into the layered cathode up to a limit of about 0.1 Ca (i.e. Na_0.47Ca_0.1Mn_0.72Mg_0.28O₂). These findings point to the intriguing possibility of achieving facile room temperature, solid-state ion-exchange in other alkali-ion systems.

离子交换是实现碱离子部分或完全取代碱离子进入碱离子电池插入阴极的重要途径。在钠离子阴极中，钠离子部分取代大的、电荷密集的柱离子，如Ca2+，可以帮助减轻这些阴极在脱盐过程中所经历的有害结构转变。通常，离子交换是通过在溶液中存在大量摩尔过量碱卤化物盐的情况下加热阴极粉末来实现的。在这里，我们成功地证明了在Na0.67Mn0.72Mg0.28O2中，通过简单的机械混合粉末和适当摩尔量的CaI2，在环境条件下Ca2+离子交换为Na+。反应在室温下的固态中进行，通过形成与空气中的水分自发形成的ca2晶体水合物。Ca2+均匀地结合到层状阴极中，达到约0.1 Ca的极限（即Na0.47Ca0.1Mn0.72Mg0.28O2）。这些发现指出了在其他碱离子系统中实现易于室温的固态离子交换的有趣可能性。

{"title":"Room temperature, solid-state Ca ion-exchange in Na0.67Mn0.72Mg0.28O2","authors":"John-Joseph Marie , Jun Chen , Shengda D. Pu , Alex W. Robertson , Robert A. House , Peter G. Bruce","doi":"10.1016/j.ssi.2025.117085","DOIUrl":"10.1016/j.ssi.2025.117085","url":null,"abstract":"<div><div>Ion-exchange is an important route to achieve partial or complete substitution of alkali ions into intercalation cathodes for alkali-ion batteries. In Na-ion cathodes, the partial substitution of Na for large, charge dense pillar ions, such as Ca2+, could help alleviate the detrimental structural transitions that these cathodes undergo during desodiation. Typically, ion-exchange is achieved by heating the cathode powder in the presence of a substantial molar excess of alkali halide salt in solution. Here, we successfully demonstrate ion-exchange of Ca2+ for Na+ in Na0.67Mn0.72Mg0.28O2 by simple mechanical mixing of powders with the proper molar amount of CaI2 under ambient conditions. The reaction proceeds in the solid-state at room temperature via the formation of crystalline hydrates of CaI2 which form spontaneously with moisture in the air. Ca2+ is uniformly incorporated into the layered cathode up to a limit of about 0.1 Ca (i.e. Na0.47Ca0.1Mn0.72Mg0.28O2). These findings point to the intriguing possibility of achieving facile room temperature, solid-state ion-exchange in other alkali-ion systems.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"434 ","pages":"Article 117085"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145623404","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Research on synthesis process and calcination reaction mechanism of porous LLZO with high specific surface area 高比表面积多孔LLZO的合成工艺及煅烧反应机理研究

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-12-01 DOI: 10.1016/j.ssi.2025.117086

Shengdong Tao , Jian Li , Yali Liu , Zulv Huang , Hui Fu , Guowen He , Kun Shen , Zheng Liu , Zhifang Yin

Garnet-type Li₇La₃Zr₂O₁₂ (LLZO), a promising solid-state electrolyte due to its high ionic conductivity, wide electrochemical window, and stability against metallic lithium, has attracted significant attention in recent years. However, its practical application is severely limited by drawbacks, including insufficient mechanical flexibility, prolonged synthesis/calcination times and challenging process control. This study proposes a metal-organic framework (MOF)-mediated strategy for LLZO synthesis. Specifically, La-Zr-MOF was constructed via hydrothermal self-assembly in solution, leveraging the strong coordination of carboxylate ligands with La³⁺ and Zr⁴⁺ ions. Subsequent incorporation of a lithium salt yields an LLZO precursor with atomic-level homogeneous dispersion of La, Zr, and Li. Direct calcination of the precursor produced phase-pure LLZO in a single step. Through process optimization, employing polyethylene glycol-200 (PEG-200) as the MOF synthesis solvent, LiAc as the lithium source, and 20 mol% lithium excess, cubic-phase LLZO with a high specific surface area (144.76 m² g⁻¹) was successfully synthesized at a relatively low temperature (1000 °C) with a short holding time (5 h). Furthermore, the calcination mechanism of LLZO was elucidated by SEM, XRD, TEM, specific surface area analysis and pore size distribution analysis of samples calcined at different temperatures. This research provides a novel strategy for the low-temperature, rapid synthesis of high-surface-area cubic-phase LLZO.

石榴石型Li7La3Zr2O12 （LLZO）具有离子电导率高、电化学窗口宽、抗金属锂稳定性好等优点，近年来受到广泛关注。然而，它的实际应用受到一些缺点的严重限制，包括机械灵活性不足、合成/煅烧时间长和过程控制困难。本研究提出了一种金属有机框架（MOF）介导的LLZO合成策略。具体来说，利用羧酸配体与La3+和Zr4+离子的强配位，通过水热自组装在溶液中构建了La-Zr-MOF。随后加入锂盐产生具有原子水平均匀分散的La、Zr和Li的LLZO前驱体。前驱体直接煅烧一步制得相纯LLZO。通过工艺优化，以聚乙二醇-200 （PEG-200）为MOF合成溶剂，LiAc为锂源，过量锂量为20 mol%，在相对较低的温度（1000℃）和较短的保温时间（5 h）下成功合成了高比表面积（144.76 m2 g−1）的立方相LLZO。通过SEM、XRD、TEM、比表面积分析和不同温度下煅烧样品的孔径分布分析，阐明了LLZO的煅烧机理。本研究为低温、快速合成高比表面积的三相LLZO提供了一条新思路。

{"title":"Research on synthesis process and calcination reaction mechanism of porous LLZO with high specific surface area","authors":"Shengdong Tao , Jian Li , Yali Liu , Zulv Huang , Hui Fu , Guowen He , Kun Shen , Zheng Liu , Zhifang Yin","doi":"10.1016/j.ssi.2025.117086","DOIUrl":"10.1016/j.ssi.2025.117086","url":null,"abstract":"<div><div>Garnet-type Li7La3Zr2O12 (LLZO), a promising solid-state electrolyte due to its high ionic conductivity, wide electrochemical window, and stability against metallic lithium, has attracted significant attention in recent years. However, its practical application is severely limited by drawbacks, including insufficient mechanical flexibility, prolonged synthesis/calcination times and challenging process control. This study proposes a metal-organic framework (MOF)-mediated strategy for LLZO synthesis. Specifically, La-Zr-MOF was constructed via hydrothermal self-assembly in solution, leveraging the strong coordination of carboxylate ligands with La3+ and Zr4+ ions. Subsequent incorporation of a lithium salt yields an LLZO precursor with atomic-level homogeneous dispersion of La, Zr, and Li. Direct calcination of the precursor produced phase-pure LLZO in a single step. Through process optimization, employing polyethylene glycol-200 (PEG-200) as the MOF synthesis solvent, LiAc as the lithium source, and 20 mol% lithium excess, cubic-phase LLZO with a high specific surface area (144.76 m2 g−1) was successfully synthesized at a relatively low temperature (1000 °C) with a short holding time (5 h). Furthermore, the calcination mechanism of LLZO was elucidated by SEM, XRD, TEM, specific surface area analysis and pore size distribution analysis of samples calcined at different temperatures. This research provides a novel strategy for the low-temperature, rapid synthesis of high-surface-area cubic-phase LLZO.</div></div>","PeriodicalId":431,"journal":{"name":"Solid State Ionics","volume":"433 ","pages":"Article 117086"},"PeriodicalIF":3.3,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145621542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Preparation of partially Y- or Yb-substituted SrFeO3-δ with cubic perovskite structure and its electrical conduction properties 立方钙钛矿结构部分Y或yb取代SrFeO3-δ的制备及其导电性能

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-21 DOI: 10.1016/j.ssi.2025.117073

Keina Nagai , Chihiro Kato , Ryutaro Maehara , Taizo Yoshino , Takayuki Sugimoto , Kosuke Shido , Takuya Hashimoto , Fumito Fujishiro , Eiki Niwa , Motoyuki Matsuo

SrFeO_3-δ prepared in air exhibits a tetragonal or orthorhombic perovskite crystal structure with an ordered distribution of oxide-ion vacancies at room temperature. Changing the crystal structure to cubic perovskite with a random distribution of oxide-ion vacancies is expected to improve the hole or oxide-ion conductivity. In this study, the crystal structure of SrFeO_3-δ was altered by partially substituting Y or Yb at the Sr or Fe sites. X-ray diffraction and X-ray absorption spectroscopy revealed that Y partially substituted only at the Sr site, whereas Yb could substitute at both the Sr and Fe sites. Both substitutions resulted in a cubic perovskite structure. Mössbauer spectroscopy detected charge delocalization from the Y- or Yb-substitution in the cubic phase. The degree of delocalization was higher in the Sr-site-substituted specimen than in the Fe-site-substituted specimen. The cubic phases of Sr_1-xY_xFeO_3-δ, Sr_1-xYb_xFeO_3-δ, and SrFe_1-xYb_xO_3-δ exhibited a semiconducting temperature dependence devoid of phase transition effects. The lower electrical conductivity of SrFe_1-xYb_xO_3-δ compared with that of Sr_1-xYb_xFeO_3-δ corresponded to the lower delocalization degree observed by Mössbauer spectroscopy. Sr_0.9Y_0.1FeO_3-δ and Sr_0.9Yb_0.1FeO_3-δ exhibited electrical conductivity comparable with that of cubic SrFeO_2.75 above 420 °C without the structural phase transition influence, indicating their application potential, e.g., for gas separation and electrodes in solid oxide fuel cells.

在空气中制备的SrFeO3-δ在室温下表现为四方或正交钙钛矿晶体结构，氧化离子空位分布有序。将晶体结构改变为具有随机分布的氧化离子空位的立方钙钛矿有望改善空穴或氧化离子的电导率。在本研究中，通过在Sr或Fe位点部分取代Y或Yb，改变了SrFeO3-δ的晶体结构。x射线衍射和x射线吸收光谱显示，Y仅部分取代Sr位，而Yb可以取代Sr位和Fe位。这两种取代都产生了立方钙钛矿结构。Mössbauer光谱检测到立方相中Y-或Y-取代的电荷离域。sr -取代样品的离域程度高于fe -取代样品。Sr1-xYxFeO3-δ、Sr1-xYbxFeO3-δ和SrFe1-xYbxO3-δ的立方相表现出半导体温度依赖性，没有相变效应。与sr1 - xybxo3 -δ相比，srfe1 - xybxfeo3 -δ的电导率较低，这与Mössbauer光谱观察到的较低的离域程度相对应。Sr0.9Y0.1FeO3-δ和Sr0.9Yb0.1FeO3-δ在420°C以上表现出与立方SrFeO2.75相当的电导率，而不受结构相变的影响，表明它们的应用潜力，例如用于气体分离和固体氧化物燃料电池的电极。

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引用次数: 0

Insights into ion transport in polymer electrolytes: Classifications, models and mechanisms 聚合物电解质中离子传输的见解：分类、模型和机制

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-19 DOI: 10.1016/j.ssi.2025.117083

Maitri Patel , Kuldeep Mishra , J.J. Chaudhari , Vaishali Madhani , Jehova Jire L. Hmar , Ashwani Kumar , Neeladri Das , Deepak Kumar

Polymer-based electrolytes have emerged as the most viable component for various electrochemical applications, including batteries, fuel cells, and supercapacitors, due to their unique combination of properties, such as competitive ionic conductivity, a high electrochemical stability window, and superior adhesion at the electrolyte/electrode interface with mechanical flexibility. To obtain the most suitable electrolyte system, these electrolyte systems have undergone through various structural and compositional modifications. There are different classes of polymer electrolytes. Understanding the ion-transport mechanisms in these complex materials is essential for optimizing their performance. This study offers a thorough examination of several models suggested for ion conduction in polymer electrolytes. The classical approaches, such as the vehicular and segmental motion models, as well as more recent theories, including the Vogel-Tammann-Fulcher (VTF) model, dynamic bond percolation, and hopping mechanisms, are discussed in detail. Emphasis is given to the interplay between polymer segmental motion and ion transport, the role of ion–polymer interactions, the role of different fillers and plasticizers, and the influence of structural heterogeneity on conduction pathways. This work also highlights the strengths and limitations of the ion conduction models.

聚合物电解质已成为各种电化学应用中最可行的组件，包括电池、燃料电池和超级电容器，因为它们具有独特的组合特性，如竞争性离子电导率、高电化学稳定性窗口以及在电解质/电极界面具有机械灵活性的优越附着性。为了获得最合适的电解质体系，这些电解质体系经过了各种结构和成分的修饰。聚合物电解质有不同的种类。了解这些复杂材料中的离子传输机制对于优化其性能至关重要。本研究对聚合物电解质中离子传导的几种模型进行了全面的研究。经典的方法，如车辆和节段运动模型，以及最近的理论，包括Vogel-Tammann-Fulcher （VTF）模型，动态键渗透和跳跃机制，进行了详细的讨论。重点是聚合物节段运动与离子传递之间的相互作用，离子-聚合物相互作用的作用，不同填料和增塑剂的作用，以及结构不均匀性对传导途径的影响。这项工作也突出了离子传导模型的优势和局限性。

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引用次数: 0

Bi-material cathodes based on O3-type NaNi1/3Fe1/3Mn1/3O2 and activated carbon for high-energy hybrid sodium ion battery capacitors 基于o3型NaNi1/3Fe1/3Mn1/3O2和活性炭的高能混合钠离子电池电容器双材料阴极

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-18 DOI: 10.1016/j.ssi.2025.117071

Hengheng Xia , Chongyang Yang , Zhongxun An , Yue-Ling Bai , Jiaqiang Xu

Hybrid sodium ion battery capacitor (SIBC) is a type of internal hybrid electrochemical energy storage device featuring a dual-energy storage mechanism, capable of delivering high energy and power densities. In this work, we have developed high-energy SIBCs using bi-material cathodes composed of NaNi_1/3Fe_1/3Mn_1/3O₂ (NFM) and activated carbon (AC), paired with presodiation-free hard carbon anodes. NFM offers high capacity but suffers from poor conductivity and rate capability, whereas AC enhances kinetics but limits energy density. Through optimization of the AC/NFM mass ratio in commercial-scale pouch-type full cells, we demonstrate that a hybrid cathode with 9.1 wt% AC (R_1/10) achieves optimal electrochemical performance. This design effectively balances battery-type (NFM) and capacitor-type (AC) materials, resulting in a significant reduction in electrode resistance from 19.4 mΩ to 10.8 mΩ, along with decreased interfacial film resistance and charge transfer resistance, thereby enhancing capacitive contribution. The R_1/10 SIBC delivers a high energy density of 161.3 Wh kg⁻¹ at 74.8 W kg⁻¹ and maintains 62.3 Wh kg⁻¹ at 11.8 kW kg⁻¹, outperforming pure NFM cells. It also exhibits enhanced low-temperature performance with 38.0 % capacity retention at −20 °C (5C), superior cycling stability with 72.2 % capacity retention after 10,000 cycles at 10C, and minimal self-discharge at 60 °C (0.5 mV h⁻¹). The synergy between AC and NFM mitigates polarization, accelerates reaction kinetics, and broadens the practical applicability of high-power energy storage systems.

混合钠离子电池电容器（SIBC）是一种具有双能量存储机制的内部混合电化学储能装置，能够提供高能量密度和功率密度。在这项工作中，我们开发了高能SIBCs，使用由NaNi1/3Fe1/3Mn1/3O2 （NFM）和活性炭（AC）组成的双材料阴极，搭配无预沉淀的硬碳阳极。NFM提供高容量，但电导率和速率能力差，而交流电提高了动力学，但限制了能量密度。通过优化商业规模的袋式全电池中AC/NFM的质量比，我们证明了9.1 wt% AC （R1/10）的混合阴极获得了最佳的电化学性能。这种设计有效地平衡了电池型（NFM）和电容器型（AC）材料，使电极电阻从19.4 mΩ显著降低到10.8 mΩ，同时降低了界面膜电阻和电荷转移电阻，从而提高了电容的贡献。R1/10 SIBC在74.8 W kg - 1时提供161.3 Wh kg - 1的高能量密度，在11.8 kW kg - 1时保持62.3 Wh kg - 1，优于纯NFM电池。它还表现出增强的低温性能，在- 20°C （5C）下容量保持率为38.0%，在10°C下循环10000次后容量保持率为72.2%，在60°C （0.5 mV h - 1）下自放电最小。AC和NFM之间的协同作用减轻了极化，加速了反应动力学，拓宽了大功率储能系统的实际适用性。

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引用次数: 0

Novel oxygen-ion conductors Ln10W22O81 (Ln = La, Ce, Pr, Nd) 新型氧离子导体Ln10W22O81 （Ln = La, Ce, Pr, Nd）

IF 3.3 4区材料科学 Q3 CHEMISTRY, PHYSICAL

Solid State Ionics

Pub Date : 2025-11-15 DOI: 10.1016/j.ssi.2025.117072

A. Guseva, N. Pestereva, V. Gardt, D. Kuznetsov

Lanthanide tungstates Ln₁₀W₂₂O₈₁ (Ln = La, Ce, Pr, Nd) were prepared by the by solid-state reaction technique and their electrical conductivity have been examined by the electrochemical impedance method. Predominant ionic conductivity in Ln₁₀W₂₂O₈₁ (Ln = La, Pr, Nd) was established both by the EMF method and from independence of conductivity versus oxygen partial pressure. Ce₁₀W₂₂O₈₁ reveals some contribution of the electronic p-type component. The Tubandt method established that the ionic charge carriers in lanthanide tungstates are oxygen ions. It was found that the electrical conductivity of the studied lanthanide tungstates decreases in the order Ce₁₀W₂₂O_81, Pr₁₀W₂₂O₈₁, La₁₀W₂₂O₈₁, Nd₁₀W₂₂O₈₁. Of all the compounds studied, praseodymium tungstate has the highest oxygen-ion conductivity (3.2 × 10⁻⁴ S/cm at 800 °C), which makes it the most promising for further research and application in solid-state ionics.

采用固相反应法制备了镧系钨酸盐Ln10W22O81 (Ln = La, Ce, Pr, Nd)，并用电化学阻抗法对其电导率进行了测试。通过电动势法和电导率与氧分压的独立关系，确定了Ln10W22O81的主要离子电导率（Ln = La, Pr, Nd）。Ce10W22O81显示了电子p型元件的一些贡献。Tubandt方法确定了镧系钨酸盐中的离子载流子是氧离子。结果表明，镧系钨酸盐的电导率依次为Ce10W22O81、Pr10W22O81、La10W22O81、Nd10W22O81。在所研究的化合物中，钨酸镨具有最高的氧离子电导率（在800°C时为3.2 × 10−4 S/cm），这使其在固态离子中具有进一步研究和应用的前景。

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